Cyano and thiocyano compounds and a process for their manufacture



Patented Sept. 17, 1940 v UNITED STATES PATENT or 2,214,971 FICE CYANO AND THIOCYANO COMPOUNDS AND A PROCESS FOR THEIR. MANUFACTURE Paul Miiller, Neu-Alischwil, near Basel, Switzerland, assignor to the firm J. R. Geigy A. G.,

Basel, Switzerland No Drawing. Application December 23, 1938, Se-

rial No. 247,586. In Switzerland December 27,

12 Claims.

This invention relates to a manufacture of a series of new cyano and thiocyano compounds,

wherein a compound of the formula (divalent) organic radical halogen ON or CNS containing exchangeablehalogen, is caused to react with ammonia or an amine.

' When ammonia or a non-tertiary amine is used there is produced by elimination of the corresponding hydrogen compound H-halogen a,

primary, secondary or tertiary compound which may be used in the form of a base or converted into a water-soluble form by means of an acid.

The primary or secondary substituted products of the reaction may be further alkylated or pounds by addition ofthe above defined compound halogen (divalent organic radical) ON or (3N S. Suitable organic divalent radicals are especially aliphatic or araliphatic radicals which may contain substituents. As amines there are of value for the reaction aliphatic, aromatic and cycloaliphatic compounds.

The new cyano or thiocyano compounds may I be used for various purposes in the-formof bases dissolved in suitable solvents, or in the form or salts or quaternary compounds dissolved in water. In part they are valuable capillary active agents,

for instance wetting, dispersing and emulsifying. I

agents. In partthey are poisons suitable-ior combating moths and other pests of the insect class; in the case of some compounds there is a specially pronounced fungicidal or bactericidal effect which exceeds that of bodies of similar composition without the CNor CNS group..

-The following examples illustrate the invention, the parts being by weight:

Example 1 12 parts of dimethylaminoacetic acid-3:4-dichloranilide (made by heating a benzene solution thioeyanate are added and the whole is boiled under reflux for 24-48 hours. The grey pulverulent substance which collects at the bottom of the vessel isflltered and purified by washing with acetone. There is thus obtaineda light-grey powder freely, soluble in water and of good fungicidal and bactericidal properties.

The following equation illustrates the reaction involved: I

c1 7 =(CHs)|.N.CHzQO.NHQCl C(JEH:

NS Example 2 '7 parts of the same base as is used in Example 1 are dissolved in 20 parts of benzene and 3 parts of u-chlorethylene-fl nltrile are added. Already after a few hours there separates afine white crystalline powder. This is filtered with suction and washed with benzene.

When dry the product is a white powder of good solubility in water.

The following equation'illustrates the reaction involved:

N Example 3 1 mol. of dimethylaminoacetic acid-4-chlorophenyl ether phenyl-4-amide (made by condensation of 1 mol. of para-nitrochlorobenzene with 1.2 mol. of para-chloro'phenol at -140" C. by adding by drops in the course of 2-4 hours causticpotash lye 01.50 per cent strength, heating for 4-5 hours at -160 0., reduction in known manner of the nitro compound thusobtained and-reaction oi the amine produced with chloracetyl chloride and dimethylamine as described in Example 1) is dissolved in benzene and caused to react with l mol. of ,p-chlorethylene thiocyanate. After heating for several days under reflux, the quaternary ammonium compound "will have-"separated in ,pulverulent form. It is filtered with suction, washed with benzeneand dried; it is then a white powderwhich dissolves clearly in water and protects woohhair, feathers,

furs, leather or the like from the attack of moth, even when used in low concentration.

The following equation illustrates the reaction involved:

(CHa)2=N.CHzCO.NHOOOCl +CICH2.CH:.CNS=

Example 4 17 parts of ,dimethylaminoacetic acid-3':4-

dichlorophenyl ether pheny1-4-amlde (made in the manner described in Example 3 with the variation that instead of para-chlorophenol 324-.

dichlorophenoi is used) are dissolved in 50 parts of benzene, 6 parts of 0:,B-ChlOIBthY1Bl'1B thiocyanate are added and the .whole is boiled under reflux for about 24 hours. The product is precipitated by adding much ether and for purification is once reprecipitated from benzene. The adherent solvent is then removed in a vacuum at 40-50 0., whereby there is obtained a spumous substance which dissolves in hot water to an opalescent solution.

The following equation illustrates the reaction involved:

(CH3)2=N.CH2C ONEQO-QCI +CICH2.CH2.CNS=

(|3H: CNS

Example 5 I 17 parts of dimethylaminoacetic acid-2:2- dichlorodiphenyl ether 4-amide (made analogously to the method described in Example 3) are -I-CICH2.CH2.CNS=

(onmdfsmcoua-Qo C(CH:

.( JNS Example 6 19 parts of dimethylaininoacetic acid-2:2:4'- trichlorodiphenyl ether-4-amide (madeas described in Example 3 by the reaction of 3:4-

dichloronitrobenzene with 2:4-dichlorophenolate and so on) are dissolved in 50 parts of benzene, 6 parts of a,fl-chlorethylene thiocyanate are addedand the whole is boiled for 24 hours under reflux. The product cannot be precipitated by any of the usual solvents, but can be obtained as a bright powder by removing the solvent; this powder is soluble in hot water, especially on addition of alcohol.

The following'equation illustrates the reaction involved:

(CHQFNbHmQNHQOQm By replacing the u,p-chlorethylene thiocyanate by the equimolecular quantity of bromoacetonitrile, a similar final product is obtained according to the above example.

Example 7 16.5 parts of afi-chlorethylene thiocyanate and 31.8 parts of dodecyldimethylamine (made in known manner from dodecyl bromide and a dimethylamine solution at 40-60 C.) are stirred with parts of benzene for 8 hours at 50 C. By addition of petroleum ether a fiocculent precipitate which cannot be filtered is. obtained. This is dissolved in water and thesolution'is evaporated in a vacuum at 50 C. The residue is a sticky, light-brown.mass soluble in water to a clear solution and having good wettin'g, fungicidal and bactericidal properties.

The following equation illustrates the reaction involved:

If instead of the a,p-chlorethylene compound an Ii-halogenated capronic acid, such as the wbromoor -jodo-capronic acid or a-bromo-capric acid is employed, similar products are obtained.

Example 8 17 parts of thebase of the formula chloracetyl chloride in benzene at 50-60 C. and heating the product of this reaction with an aqueous dimevth'ylamine. solution of 20 per cent strength) are dissolved in 50 parts of benzene and 6 parts of a,p-chlorethylene thiocyanate are added. The whole is boiled for 48 h0urs and petroleum ether is added to precipitate the product. The latter is washed with ether and freed from solvent in a vacuum. It is a tough brown mass which dissolves to a turbid solution in water. I

The following equation illustratesthemaction involved:

H: Example 9 17 parts of dimethylaminoacetic acid dodecyl anilide (made from commercial dodecyl alcohol known as Lorol and aniline in slight excess by heating the mixture until the calculated quantity or water is distilled and causing the product to react with chloracetyl chloride and dimethylamine in known manner) are dissolved in 50 parts of v benzene, 6 parts of a,p-chlorethylene thiocyanate are'added and the whole is boiled ior 14 hours. By adding petroleum ether, washing the precipitate produced and drying it in a vacuum, there is obtained a brownish semi-solid mass which dissolves in water to a clear solution and acts as a very strong fungicide.

The following equation illustrates the reaction involved:

(CHa)a=N.OHaC O.N.C12Hat H1.CH:ONB Example 10 17 parts of dlmethylaminoacetic acid dodecylvanilide are dissolved in 50 parts of benzene, 7.5

parts of paracyanobenzyl chloride (or bromide) are added and the whole is boiled for 3-5 hours.

Petroleum ether is then added and the precipitate water too. clear solution and having good fungicidal and bactericidal properties.

The following equation illustrates the reaction involved ormFNcmcoummwowm-Ocn Example 11'. I

10 parts of dimethylaminocyclohenane; made by hydrogenating dimethylaniline, are dissolved in 50 parts of benzene and 10 parts of afi-ODIOI- ethylene thiocyanate are added. The whole is boiled for4-5 hours and the precipitateproduced by adding petroleum ether is filtered with suction. It is a white crystallized body which dissolves clearly in water;

The following'equation illustrates the reaction I A similar compound is obtained by using as starting material hydrogenated dimethyl-mtoluidine.

anilide are dissolved in 50 parts of benzene and 6 parts of phenylchloracetonitrile CsHsCHCLCN, (or an equimolecular quantity of the bromocompound) made in known manner from mandelic acid nitrile, are added. After about hours the product is precipitated by adding 'petroleum ether, the precipitate is subsequently thoroughly washed with the same solvent and then it is dried in a vacuum. It is soluble in water to a turbid solution.

The following equation illustrates the reaction involved:

(orm mcmconcmwmgnG cno ncmconcnna Example v13 9 .parts of ,p-chlorethylene cyanide and parts of methyl aniline are heated together for 14-16 hours at 110-120 C. The mass has then become semi-solid. Water is added and the whole is neutralized with sodium bicarbonate. The

separated mixtureof bases is dissolved in ether, the ethereal solution is separated and distilled in a vacuum. The new base having the formula:

and a boiling point under iii- 14 millimetres pressure at 165-170 0., is obtained in the form of a thick yellowish oil. It may be'dissolved in an stance hydrochloric acid, sulphuric acid or silicohydroiluoric acid, whereby it is obtained in the form suitable for use.

organic solvent or neutralized with acids, for in-. i

If the w-cyanethyl methylaniline is caused to react in known manner with dimethyl sulphate in benzene, there is obtained the quaternary compound in the form of a thick honey-like mass. It dissolves clearly in water and has both fungicidal and bactericidal effects.

'The following equation illustrates the reaction involved:

. /CH| NBLCH! N omomcN on. -CH;

The same compound is obtained if aniline is used instead of methyl aniline and if the inter- -mediate product is completely methylated. Similar compounds are obtained by starting from the toluidines, xylidines or naphthylamines. The tertiary alkylated bases may also be converted into the quaternary compounds by means of aralkylating agents, such as benzylchloride.

Example 14 12 parts of a,p-chlorethylene thiocyanate are heated together with 30 parts of ethyl aniline for 14-16 hours'at 11Q-130 C. and the mass isworked up'in the manner described in Example 13. The newcompound distlls in a vacuum of 3 millimetres at 160-175" C. It may be used in the form of base or in aqueous solution united to acids.

By ethylating with diethylsulphate in benzene solution the ammonium compound is produced. It is soluble to a clear solution in water.

The following equation illustrates the reaction involved:

CzHs

NHLC H CHaCHaCNS In the same manner, as indicated in Example 13, one may start from aniline to produce the w-thiocyanethylan'iline and exhaustively ethylate, for example with diethylsulphate, thus obtaining the same quaternary compound.

With other primary or secondary organic amines or NH: there may be obtained as described in Examples 13 and 14, the corresponding bases,

their salts and quaternary compounds in large number.

What I claim is:

1. A process for the manufacture of cyano and thiocyano compounds, comprising causing a compound corresponding to the general formula Halogen--R.-Y wherein halogen means an exchangeable halogen atom, R means a divalent organic radical selected from the group consisting of aliphatic and araliphatic radicals, and Y means one of CN and CNS radicals, to react with a nitrogen compound selected from the group consisting of NHa, primary, secondary andtertiary aliphatic, cycloaliphatic and aromatic amines.

2. A process for the manufacture of cyano and thiocyano compounds, comprising treating compounds of the general formula wherein R1 and R2 mean radicals selected from the group consisting of aliphatic and aromatic radicals of the benzene series, B. means 'a divalent organic radical selected from the group consisting of aliphatic and araliphatic radicals, and Y gen compound selected from the group consistphatic,' cycloaliphatic and aromatic amines.

4. A process for the manufacture of thiocyano compounds, comprising causing u,p-chlorethylenethiocyanate to react with dodecyldimethylamine. I

5. A process for the manufacture of thiocyano compounds, comprising causing a, 3-chlorethyl'- enethiocyanate to react with. an amide of a dialkylamino-acetic acid selected from the group of aliphatic and aromatic amides.

6. A process for the manufacture of thiocyano compounds, comprising causing ufi-chlorethylenethiocyanate to react with dimethylaminoacetic acid 2:2 :4'- trichlorodiphenylether 4- amide f the formula.

7. A process for the manufacture of thiocyano compounds, comprising causing a,c-chlorethylenethiocyanate to react with dimethylaminoacetic acid dodecylanilide. V

8. As new products, the bases of the general formula R1-1\IRY wherein R1 and R2 mean radicals selected from the group consisting of aliphatic and aromatic radicals of the benzene series, R'means a divalent 'ing of NH3, primary, secondary and tertiary aliorganic radical selected from the group consisting of aliphatic and araliphatic radicals and Y means one of the group consisting of CN and CNS radicals,; and their soluble salts and quaternary compounds.

11. As a new product the compound of the 9.Aanewproductcthebaeelotthegeneral formula B. Br-l -O Ha -O Ha-Y 15 cm Owls- 01 on. canons 20 being a sticky, light brown mass soluble in water to a clear eolution and having good wetting, fungicidal and bactericidal properties.

formula I \z omcorm o 01 O a CaHeCNB l l being a bright powder soluble in hot water, es-

pecially on addition of alcohol fungicidal properties.

and having good 12. As a new product the product the com pound of the formula om c1 \fcmooJII-O a lHl-CNB 0 a alkyl meaning the alkyl radical of commercial dodecyl alcohol. being a brownish. oemi-lolid mass which dissolves in water to a clear lolution acting as a very strong fungicide.

m1. HOLLIS. 

